Maria Strømme

Toward Flexible Polymer and Paper-Based Energy Storage Devices

All-polymer and paper-based energy storage devices have significant inherent advantages in comparison with many currently employed batteries and supercapacitors regarding environmental friendliness, flexibility, cost and versatility. The research within this field is currently undergoing an exciting development as new polymers, composites and paper-based devices are being developed. In this report, we review recent progress concerning the development of flexible energy storage devices based on electronically conducting polymers and cellulose containing composites with particular emphasis on paper-based batteries and supercapacitors. We discuss recent progress in the development of the most commonly used electronically conducting polymers used in flexible device prototypes, the advantages and disadvantages of this type of energy storage devices, as well as the two main approaches used in the manufacturing of paper-based charge storage devices.

Ultrafast All-Polymer Paper-Based Batteries

Conducting polymers for battery applications have been subject to numerous investigations during the last two decades. However, the functional charging rates and the cycling stabilities have so far been found to be insufficient for practical applications. These shortcomings can, at least partially, be explained by the fact that thick layers of the conducting polymers have been used to obtain sufficient capacities of the batteries. In the present letter, we introduce a novel nanostructured high-surface area electrode material for energy storage applications composed of cellulose fibers of algal origin individually coated with a 50 nm thin layer of polypyrrole. Our results show the hitherto highest reported charge capacities and charging rates for an all polymer paper-based battery. The composite conductive paper material is shown to have a specific surface area of 80 m2 g−1 and batteries based on this material can be charged with currents as high as 600 mA cm−2 with only 6% loss in capacity over 100 subsequent charge and discharge cycles. The aqueous-based batteries, which are entirely based on cellulose and polypyrrole and exhibit charge capacities between 25 and 33 mAh g−1 or 38−50 mAh g−1 per weight of the active material, open up new possibilities for the production of environmentally friendly, cost efficient, up-scalable and lightweight energy storage systems.

A Nanocellulose Polypyrrole Composite Based on Microfibrillated Cellulose from Wood

It is demonstrated that it is possible to coat the individual fibers of wood-based nanocellulose with polypyrrole using in situ chemical polymerization to obtain an electrically conducting continuous high-surface-area composite. The experimental results indicate that the high surface area of the water dispersed material, to a large extent, is maintained upon normal drying without the use of any solvent exchange. Thus, the employed chemical polymerization of polypyrrole on the microfibrillated cellulose (MFC) nanofibers in the hydrogel gives rise to a composite, the structure of which—unlike that of uncoated MFC paper—does not collapse upon drying. The dry composite has a surface area of ∼90 m2/g and a conductivity of ∼1.5 S/cm, is electrochemically active, and exhibits an ion-exchange capacity for chloride ions of 289 C/g corresponding to a specific capacity of 80 mAh/g. The straightforwardness of the fabrication of the present nanocellulose composites should significantly facilitate industrial manufacturing of highly porous, electroactive conductive paper materials for applications including ion-exchange and paper-based energy storage devices.

A Novel High Specific Surface Area Conducting Paper Material Composed of Polypyrrole and Cladophora Cellulose

We present a novel conducting polypyrrole-based composite material, obtained by polymerization of pyrrole in the presence of iron(III) chloride on a cellulose substrate derived from the environmentally polluting Cladophora sp. algae. The material, which was doped with chloride ions, was molded into paper sheets and characterized using scanning and transmission electron microscopy, N 2 gas adsorption analysis, cyclic voltammetry, chronoamperometry and conductivity measurements at varying relative humidities. The specific surface area of the composite was found to be 57 m (2)/g and the fibrous structure of the Cladophora cellulose remained intact even after a 50 nm thick layer of polypyrrole had been coated on the cellulose fibers. The composite could be repeatedly used for electrochemically controlled extraction and desorption of chloride and an ion exchanging capacity of 370 C per g of composite was obtained as a result of the high surface area of the cellulose substrate. The influence of the oxidation and reduction potentials on the chloride ion exchange capacity and the nucleation of delocalized positive charges, forming conductive paths in the polypyrrole film, was also investigated. The creation of conductive paths during oxidation followed an effective medium rather than a percolative behavior, indicating that some conduction paths survive the polymer reduction steps. The present high surface area material should be well-suited for use in, e.g., electrochemically controlled ion exchange or separation devices, as well as sensors based on the fact that the material is compact, light, mechanically stable, and moldable into paper sheets.

Sensitive molecular diagnostics using volume-amplified magnetic nanobeads

In this letter, we demonstrate a new principle for diagnostics based on DNA sequence detection using single-stranded oligonucleotide tagged magnetic nanobeads. The target DNA is recognized and volume-amplified to large coils by circularization of linear padlock probes through probe hybridization and ligation, followed by rolling circle amplification (RCA). Upon hybridization of the nanobeads in the RCA coils, the complex magnetization spectrum of the beads changes dramatically, induced by the attached volume-amplified target molecules. We show that the magnetization spectrum of the nanobeads can be used for concentration determination of RCA coils down to the pM range, thus creating the opportunity for nonfluorescence-based cost-efficient high-sensitivity diagnostics tool. We also show that the bead incorporation in the coils is diffusion-controlled and consequently may be accelerated by incubating the sample at higher temperatures.

Surface Modified Nanocellulose Fibers Yield Conducting Polymer-Based Flexible Supercapacitors with Enhanced Capacitances

We demonstrate that surface modified nanocellulose fibers (NCFs) can be used as substrates to synthesize supercapacitor electrodes with the highest full electrode-normalized gravimetric (127 F g(-1)) and volumetric (122 F cm(-3)) capacitances at high current densities (300 mA cm(-2) ≈ 33 A g(-1)) until date reported for conducting polymer-based electrodes with active mass loadings as high as 9 mg cm(-2). By introducing quaternary amine groups on the surface of NCFs prior to polypyrrole (PPy) polymerization, the macropore volume of the formed PPy-NCF composites can be minimized while maintaining the volume of the micro- and mesopores at the same level as when unmodified or carboxylate groups functionalized NCFs are employed as polymerization substrates. Symmetric, aqueous electrolyte-based, devices comprising these porosity-optimized electrodes exhibit device-specific volumetric energy and power densities of 3.1 mWh cm(-3) and 3 W cm(-3) respectively; which are among the highest values reported for conducting polymer electrodes in aqueous electrolytes. The functionality of the devices is verified by powering a red light-emitting diode with the device in different mechanically challenging states.

Electroactive nanofibrillated cellulose aerogel composites with tunable structural and electrochemical properties

This work presents conductive aerogel composites of nanofibrillated cellulose (NFC) and polypyrrole (PPy) with tunable structural and electrochemical properties. The conductive composites are prepared by chemically polymerizing pyrrole onto TEMPO-oxidized cellulose nanofibers dispersed in water and the various nanostructures are obtained employing different drying methods. Supercritical CO2 drying is shown to generate high porosity aerogel composites with the largest surface area (246 m2 g−1) reported so far for a conducting polymer–paper based material, whereas composites produced by ambient drying attain high density structures with mechanical properties significantly surpassing earlier reported values for cellulose–conducting polymer composites when normalized with respect to the content of reinforcing cellulose (Youngs modulus = 0.51 GPa, tensile strength = 10.93 MPa and strain to failure = 2.5%). Electrochemical measurements clearly show that differences in the porosity give rise to dramatic changes in the voltammetric and chronoamperometric behavior of the composites. This indicates that mass transport rate limitations also should be considered, in addition to the presence of a distribution of PPy redox potentials, as an explanation for the shapes of the voltammetric peaks. A specific charge capacity of ∼220 C g−1 is obtained for all composites in voltammetric experiments performed at a scan rate of 1 mV s−1 and this capacity is retained also at scan rates up to 50 mV s−1 for the high porosity composites. The composites should be applicable as electrodes in structural batteries and as membranes in ion exchange applications requiring exchange membranes of high mechanical integrity or high porosity.

Voltammetry on fractals

New methods are introduced for determining the fractal dimension df of a surface from cyclic voltammograms. The separation between current peaks is strongly dependent on df, provided that the current is diffusion limited. We also derive a new Randles-Sevcik equation-relating the diffusion coefficient to the peak current of a voltammogram—that holds for electrodes with fractal surfaces. This equation gives a simple additional method of determining df from voltammetry using recordings of the peak current at different scan rates.

Translational study between structure and biological response of nanocellulose from wood and green algae

The influence of nanostructure on the cytocompatibility of cellulose films is analyzed providing insight into how physicochemical properties of surface modified microfibrillated cellulose (MFC) and Cladophora nanocellulose (CC) affect the materials cytocompatibility. CC is modified through TEMPO-mediated oxidation and glycidyltrimethylammonium chloride (EPTMAC) condensation to obtain anionic and cationic nanocellulose samples respectively, while anionic and cationic MFC samples are obtained by carboxymethylation and EPTMAC condensation respectively. Films of unmodified, anionic and cationic MFC and CC are prepared by vacuum filtration and characterized in terms of specific surface area, pore size distribution, degree of crystallinity, surface charge and water content. Human dermal fibroblasts are exposed to culture medium extracts of the films in an indirect contact cytotoxicity test. Moreover, cell adhesion and viability are evaluated in a direct contact assay and the effects of the physicochemical properties on cell behavior are discussed. In the indirect cytotoxicity test no toxic leachables are detected, evidencing that the CC and MFC materials are non-cytotoxic, independently of the chemical treatment that they have been subjected to. The direct contact tests show that carboxymethylated-MFC presents a more cytocompatible profile than unmodified and trimethylammonium-MFC. TEMPO–CC promotes fibroblast adhesion and presents cell viability comparable to the results obtained with the tissue culture material Thermanox. We hypothesize that the distinct aligned nanofiber structure present in the TEMPO–CC films is responsible for the improved cell adhesion. Thus, by controlling the surface properties of cellulose nanofibers, such as chemistry, charge, and orientation, cell adhesion properties can be promoted.

A ceramic drug delivery vehicle for oral administration of highly potent opioids.

Pellets composed of the ceramic material Halloysite and microcrystalline cellulose were synthesized with the aim of producing a drug delivery vehicle for sustained release of the opioid Fentanyl with low risk for dose dumping at oral intake of the highly potent drug. Drug release profiles of intact and crushed pellets, to simulate swallowing without or with chewing, in pH 6.8, pH 1, and in 48% ethanol were recorded in order to replicate the conditions in the small intestines, in the stomach, as well as cointake of the drug with alcohol. The drug release was analyzed by employing the Weibull equation, which showed that the release profiles were either governed by fickian diffusion (intact pellets in pH 6.8 and in ethanol) or by diffusion in a fractal or disordered pore network (intact pellets in pH 1 and crushed pellets in all solutions). A sustained release for approximately 3-4 h was obtained in all studied solutions from intact pellets, whereas crushed pellets released the drug content during approximately 2-3 h. The finding that a sustained release profile could be obtained both in alcohol and after crushing of the pellets, shows that the ceramic carrier under investigation, at least to some extent, hampers dose dumping, and may thus be a promising material in future developments of new opioid containing oral dosage forms.